Refining canadian or similar petroleum



(No Model.) 2 Sheets-Sheet 1.

HfFR-ASOH.

REFINING CANADIAN 0R SIMILAR PETROLEUM. No. 543,619; Patented July 30, 1895.

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I A -H. FRASGH. REFINING CANADIAN OR SIMILAR PETROLEUM.

No; 543,619. Patentd July so, 1895.

MWf/MA UNITED STATES PATENT OFFICE.

HERMAN FRASCH, OF CLEVELAND, oHio, ASSIGNOR TO. THE SOLAR REFINING COMPANY, OF OHIO.

REFINING CANADIAN ORCSIMILAR PETROLEUM.

SPECIFICATION forming part of Letters Patent No. 543,619, dated '3 30, 1895.

Original application filed I'ebruaryIB, 1888, Serial No. 264,131. Divided and this application filed January 25, 1891. Serial v No. 378,818. (No specimens.)

To all whom it mag concern.-

Be it known that I, HERMAN FRASCH, a citizen of the United States, residing at Cleveland, in the county of Cuyahoga and State of 5 Ohio, have invented certain new and useful Improvements in Refining Canadian orsimilar Petroleum, of which the following specification is a full, clear, and exact description. This invention relates to the treatment of I O Canadian and similar petroleum-such, for' example, as that found at Lima, Ohio. This oil requires a difierent treatment from the ordinary American-oil, because of the sulphur compouuds'which it contains and which give I 5 it its penetrating disagreeable odor and render it'uufit for burning in lamps unless do prived of said compounds. The sulphur is present in these oils in considerable .Tproportions-Say upward of one-half of one per cen- 2o tum of- 1t%)mo stl y in chemical combination, and some at leastofthe sulphur compounds are essentially .dilferent from those which occur in other oils and are retained with greattenacity. These'pe'culiar sulphur 2 5 compounds have received among the workers in the oil of this class the suggestive name of skunk. -'lo deprive these oils of their peculiar sulphur compounds or skunk isthe object of the present invention. The large proportion of sulphur will generally distinguish Canadian and sin ilar skunkbearing petroleum from other oils, but a further distinction may be found in the nature of the sulphur-containing bodies therein.

They give to the oils the property of dissolving lead-0xide, (litharge) So far as Lani aware no mineral oil wh ether undistilled or distillate, other than Canadian or similar skunk-bearing petroleum possesses thispropo erty of dissolvinglitharge. Ordinarily petroleum can be made to dissolve'litharge by the addition-to said oil of a fat acid, such as oleic' acid or'rosin, but the Canadian or skunkbearing pretroleuin will dissolve lead-oxide 5 (litharg'e) without suchaddition. Further,

the skunk-bearing oil has a peculiarly badodor, whichdisappears on saturating the oil with-lead oxide. On precipitatingjthe lead from such solution by means of -sulphur,the-

bad odor does not reappear, neither does the oil regain the property of dissolving lead-oxide. On distillation, however, of the oil from which the lead has been precipitated, as just described, the malodor reappears and the oil will again dissolve lead-oxide, showing that the skunk-remaine'deven after the malodor disappeated application of the skunk-removing 7o process fails to eliminate it or materially to reduce its proportion, while it can be separated almost entirely-by treatment with sulphuric acid. Skunk-bearing oil therefore is radically different from other mineral oils in respect to the sulphur bodies therein,said bodies 7 giving to the skunk-bearing oil peculiar properties, as hereinbefore mentioned, and being .not removable hy the retiniug'meansin commen use which do-remove the sulphur from Re American petroleum, while at the same time means eflicient to remove skunk do not take out sulphur bodies removable by said refining means in common'use on American oil, 7 so that the utility of certainreagents or modes 1 oftreatment in desulphurizin g other mineral -oils is ,po proof of an ability to remove the skunk of Canadian and similar petroleum,-

nor does an abilityto remove skunk constituteproof of a given process being capable go of replacing the ordinary means ofdesulphurizing oil. t. p

Heretofore it has been customary in Canadian refineries .(and the'same treatment has been employed in parts of the United States) 5 to take the burning-oil distillate, which has been subjected to the action of sulphuric acid and Washed with water, and to treat the same with 'a solution of plumbate of soda in order to deodorize it, and then to add sulphur'iu roe the plumbate solution has turned to a yellow or brown and cause the precipitation of the lead, leaving the oil above it white and clear.

The solution of soda settles to the bottom.

The objections to this old deodoriziug process are twofold: First, an excess of sulphur is liable to be added in the second stage, which is injurious to the oil, and, secondly, the treatment is not thorough, for it does not remove the sulphur compounds or skunk, but only renders the same inodorous and incapable of further uniting with the lead oxide of the plumbate solution. On distillation the sulphur compounds in the oil again became malodorous and the oil is discolored by the addilion of the plumbate of soda solution.

In a prior application filed February 21, 1887, and serially numbered 228,403, (on which Patent No. 378,246 was granted me February 21, 1888,) I have described a process not open to these objections for refining oil of the Canadian or Lima classby distilling the same with suitable oxides or compounds mixed with or dissolved in the oil under treatment. The present invention is, as it were, a supplement to or complement of that process. I have discovered that the refractory sulphur compounds or skunk of Canadian and similar oils are decomposed by suitable metallic oxides or compounds without necessarily having such an oxide or compound dissolved in or mixed with the oil in distillation by subjecting the vapors after leaving the liquidoil to the action of the said oxides or their compounds in an undissolved condition.

The carrying on of the process of purification by acting upon the vapors after they have left the oil in or from which the said vapors have been generated possesses advantages over the process described in my said patent. One advantage consists in the ability to remove skunk from the vapors of crude oil without experiencing any difficulty from the presencaot' solid matter in the tar. The tar being mixed with the residue to be revivified leaves an unnecessary mass of combustible matter in such residue. The presence of solid materialin the oil in the still moreover gives rise, irrespective of the question of the tar, to difiiculties which are not necessarily attendant on an outside vapor treatment, since this does not require the presence of solid matter in the oil. The vapors may be brought into contact with the undissolved oxides or compounds in any ordinary or suitable way. The undissolved oxide or compound may be injected into the vapors or be showered through the vapors, or vapors may be passed through the oxide or compound supported on shelves or other suitable supports in a dry state or more or less saturated with a liquid.

The oxides of lead, bismuth, cadmium, mer

cur copper, and silver are well suited to the purpose. Ferric, stannic, and antimonic ox- 1des,cuprous oxide, and the oxides of nickel,

cobalt, manganese, and zinc are of little'value by themselves, but may be used in connection with those first mentioned. Suitable compounds are the readily decomposable oxygen compounds or oxygen salts in general of the metals which are precipitable by hy-' drogen sulphide in acid solution, such as the carbonates, nianganates, chromates, borates, sulphates, and the like of such metals.

The vapors to be treated in accordancewith the present invention can be generated from the crude oil' or from any desired distillate. The purification or refining is, however, specially intended for burning oil having a boiling-point of 212 Fahrenheit or over.

The liquid condensed fromthe vapors whichhave thoroughly been brought into contact with the oxide or compound, so as to give it opportunity to act upon all the sulphur compounds or skunk will stand the plumbate of soda test. I find, however, that the condensed liquid or distillate purified from skunk, although it will stand the plumbate of soda test, yet contains sulphur compounds which I believe to be peculiar to oil treated in this way and which impair the value of the oil by causing a chimney-deposit when burned in a lamp. These products, like the similar or identical ones from distilling the oil with the purifying oxide or compound mixed with or dissolved in the same, .are essentially dilferent from skunk and are, as I have discovered, removable by treatment with sulphuric I00 acid, washing with water, and neutralizing as customary in refining American petroleum.

The metallic sulphur compounds which are formed by the reaction with the sulphur-containing impurities of the vapors, as above set 105 forth, can be revivified by roasting and oxidation, and these revivified residues can be employed successfully to treat new vapors of Canadian or Lima or similar skunk'bearing oil.

In my original application, Serial No. 264,131, filed February 15, 1888, of which the present application is a division, description was given of the removal of skunk from petroleum by subjecting the skunk-bearing var 15 pors after they had been given olI to the action of an oily or resinous liquid holding the oxides or compounds in solution or solution and suspension, as well as by subjecting such vapors to the actlonof the undissolved oxides. r 20 or compounds. After the filing of the present divisional application the said original application was so amended that Letters Patent No. 487,119 were granted thereon November 29, 1892, for the process of using the oily or resinous liquid holding the metallic oxides or compounds in solution or solution and suspension therein.. The apparatus shown in the accompanying drawings is more particularly intended for use with such oily and resinous liquid holding the metallic oxides or com poundsin solution or solution and suspension, but (modified as explained below) it may be used with the unsolved oxides or compounds.

I Fig. I is a sectional view of an oil still and purifien- Fig.'II is a similar View of a slightly modified form of the same apparatus, and Fig. III is a similar view'of another form of apparatus.

" Referring to Figs. I and II, an ordinary still A' is provided with a column B which has baffle plates ortrays and stirrers, as common or at least known in various chemical arts. In Fig. I the baffle-plates 2 are in the form of circular disks, which are mounted horizontally on an with the column B, ter there is a pipe upright central shaft 3, and the baffle-plates4 are in the form of rings fastened to the walls of the column B and projecting inward between the disk plates 2. In Fig. II the trays 5 are fastened to the walls of the column, and the openings for the passage of the vapors are formed at the opposite sides of alternate trays, and the shaft 6 is provided with stirrers which dip into the trays. In all the figures the top of the still A is connected by a vapor-pipe 7 and at the top of the lat- 8 for conveying the purified vapors to the condenser. (Not shown.) A pipe 9 leads-from the base ofthe column B to the pump 0, and a pipe 10 from the said pump 0 to the top of said column. The shafts 3 and 6 are rotated by bevel-gear, and the column B, which rests on a pillar 11, is heated by the products of combustion from the tirechamber D under the still on their way to the chimney E. The column B should be of such sizeas to bring the vapors sufficiently into contact with the purifying material. If the vstill be such as commonly used to distill a charge of one hundred barrels of oil, the column B maybe, say, ten feet high and four feet in diameter with the bathe-plates or trays about six inches apart.

In operation the still may be charged with, say, one hundred barrels of oil composed of, say, fifteen per centum of heavy oil of from 36 to 39 Baum and the remainderburning oil distillate boiling at 212 Fahrenheit or over. For working with the oily or resinous solution, as "in my said Patent No. 487,119, the column may barrels of heavyimpure orskunk-bearing (Janadianor similar oil, mixed with,- say, onebarrel of rosin, five hundred pounds of plum-- bio oxide, (litharge,) one thousand pounds of cupric oxide, (black 'oxide,) and one thousand olT through the pipe 9 the oilholding the oxpoundsof plaster-of-paris, the oxides and plaster being'finely groundand bolted. The rosin and part of the oxides'di ssolve in the oil and the rest of theoxides and-plaster are kept in suspension therein. The oil with the matter in solution and suspension therein flows over the" bafile plates or trays, which trays become filled and collect in'the of thecolumn B. Afteror before the oil is introduced the pump is'started, which draws ide-insolution and suspension therein and retu-rnsit to, the top of thecolumn Bthrough the pipe 10. The shaft 3 in the column is also rotated. The rotation of the'disk s 2,

I blade or paddle pension, said liqui be supplied with, say, five bottom being sufficient to sweep away the solid pa'rticles; but, if desired, mechanicaldevices or scrapers could be employed to sweep or -arape the surfaces of the baffleplates, as well known in chemical apparatus, wherein gases or vapors are to be brought into contact with liqids holding solid particles in suspension therein. The rotation of the shaft 3 also keeps the material stirred up in the bottom of the column B by means of an ordinary The rotation of the shaft 6, Fig. II, keeps the material stirred up in the trays 5 and at the bottom of the column. The stillA and the column B and the pump 0 and shaft 3 or 6 incolumn B being started, the still A and column B are heated, the former to evaporate the burning oil therein and the latter to prevent or diminish the condensation of the vapors from the still. The vapors pass through the pipe 7 into the lower part of column B, through which they then pass upward, and are in their pas sage brought into intimatecontact with the liquid holding the oxides in solution and sus-' with the oxides flowing in the opposite dire tion over the battle plates or trays and falling from one to the other through the rising vapors. The vapors es cape by the pipe 8 to the condenser. The passage ofthe vapors through or over the liquid enables the oxides to act on the skunk in said vapors with the formation of metallic compounds which remain in the liquid and certain new bodies which pass of with the. vapors. A constant stream of the oil having the oxides dissolved and suspended therein is introduced at the top of the column B and drawn off atthe base. The liquid drawn ofi is returned to the column,the whole or a portion of the precipitated or solid matter in suspen-" sion being removed and replaced by fresh'oxides at each round or from ti me toti me. As the metal of the oxides in solution combines with the sulphur'of the skunk and become insol'u-'- ble fresh oxide entersthesolution, the same being suppliedjfrom the matter in'fsuspen'sion.

The still is or may be supplied continuously or from time to'time.

It is not necessary t'ohave the column B .heated otherwise than by its proximity to the, still A and the passage through it of the va-' 'porsfrom said still; but in that case the con being charged red densed vapors must be taken care 'ot',"ei't her by returning them to the still or otherwise. If solid matter is allowed in the still,jeither by entering in that state from the column. B or bv precipitation in the still, the lattershould be an agitator'to keep-'it'from' setprovided with tling.

The'plumbic orthe'cupric'oxide could be used alonesay thirty-three hundredpounds ofplumbic oxide or twelvefhundred pounds of cupric oxide-or one or both could be replaced'by or used 'in' connection with another or others of the specified agents. The plaster and the resin may be omitted.

For working with undissolved oxides or compounds no liquid need be used, but the powdered oxide or compound may be fed through the purifier-column B, being withdrawn at the bottom and returned at the top by well-known conveyors.

According to another plan of working (see Fig. III) the still A is provided inside with a large pipe F, which communicates with the interior of the still through the opening 15, and also with a small column G, such as used in rectifying alcohol on top of the still, and with a small vessel ,or receiver'lfi inside the still. A steam-injector or steam-jet aspirator and compressor II sucks the vapors from the upper part of the still A and forces them througlmthe pipe Finto the bottom of the column G. The injector II also forces into the pipe F and among the vapors therein the purifying oxide or compound finely divided and in the form of a powder. The arrangement shown for supplying the injector with purifying material is intended for use with an oily or resinous solution holding the oxide or compound in suspension, and consists of a reservoir provided with a stirrer 17 and connected with the injector II by a small supply-pipe. More or less of the oxide is forced with the vapors into the column. What does not so pass is carried into the small vessel or receiver 16, the object of which is to keep the sediment from the bottom of the still. This material could be allowed to run into the still, but in that case the latter should have an agitator; or it could be discharged outside of the still, to be returned or otherwise disposed of. The column G has an overfiow at the bottom, which discharges into the receiver 16. The oil or condensed vapor in this receiver is volatilized again and passes in vapor form into the pipe F, and then into the column G. The large pipe F may have an opening into the vapor-space at each end,

so as to circulate the vapors through the pipe, as well as force them into the column G. The steam-jet to force the vapors could be used in the arrangements described with reference to Figs. I and II. Other modes of bringing the vapors into contact with the purifying agents have been indicated in the first part of this specification;

The larger the proportion of vsku-ik in the oil the (more thoroughly should the vapors be brought into contact with the purifying agents; and if the process is carried on by batches-that is,without a constant renewal of the oxide or compound-care should betaken to have the amount of purifying agent larger than'necessary to decompose all the skunk. The weight of oxides given when used'insolution or solution and suspension in an oily or resinous liquid would be ample for one hundred barrels of oil containing about-one- ...half of.one pencentum ofsnlphur.

The vapors from the purifying apparatus are received in a condenser (not shown) and the condensed liquid is washed with sulphuric acid, or it may be used without such washing.

The solid sulphur-containing residue from the above operation or from an analogous operation is roasted and oxidated, and after grinding and bolting is used like fresh oxide.

In order to revivify the purifying agent or agents the solid residue is thrown into the front part of a roasting-furnace a portion at a time and ignited. The combustion of the sulphur-containing residue furnishes all the heat necessary for roasting. The air will supply the oxygemso as to elfect the revivification at one operation. As each fresh portion is added the portions previously introduced are pushed back until the whole charge has been transferred to the furnace. The mass becomes red hot and is thoroughly roasted and oxidated. The fine division of the powder and its composition insures a perfect and quick roasting. It is stirred until below red heat, and is then discharged to be rcground for use again.

I do not claim herein the apparatus described. It forms the subject of my application, Serial No. 289,746, filed November 1, 1888, on which Letters Patent No. want were granted January 17, 1893; nor do I claim herein the revivifieation of the residue of the revivified residues, as such matter forms the subject of my application; Serial No. 28'1t,830, filed September 7, 1 888, on which Letters Patent No. 500,252 were granted June 27, 189 3;

but the use of the revivi tied residues, as here-.

in described, is included in the present invention; nor do I claim herein what I have claimed in my before-mentioned patent, No. 487,119, dated November 29, 1892.

It will be understood that the invention is not restricted to the precise numbers given in the foregoing description, nor to other de tails of the process, nor to apparatus, but that these are describeihby way of illustration and example.

I claim he ein as my invention or discovcry-- 1. The process of removing the sulphur compound termed skunk from Canadian and similar petroleum, which consists in vaporizing the oil and subjecting the skunkbearing vapors given off from the body of oil to the action in an undissolvcd condition of one or more of the oxides or oxygen salts of the metals of that class which are precipitated by hydrogen sulphide in acid solution and which form oxides soluble in skunk-bearing oil; substantially as described.

2. The process of-removing the sulphur compound termed skunk from Canadian and similar petroleum, which consists in vaporizing the oil and subjecting the skunk-bearing vapors given off from the body of oil to the action in an undissolved condition of showers, films, or spray of one or more of the oxides or oxygensalts of .the metals of that. class which are prccipitate'd'by hydrogen sel phide in acid solution and which form oxides soluble in skunk-bearing oil; substantiallyas described.

3. .The process of refining Canadian or si milar skunk-bearing petroleum, which consiststion and which form oxides soluble in skun'kbearing oil, condensing the vapors from which the sulphur compound termed skunk has thus been removed, and washing the condensed liquid with sulphuric acid; substantially as described.

4. The process of removing the sulphur compound'terlned skunk from Canadian and similar petroleum, which consists in vaporizing the oil and subjecting the skunk-bearing vapors given 01? from the body of oil to the action in a drystate of one or more of the oxides or oxygen salts of the metals of that class which are precipitated by hydrogen sulphide in acid solution and which form oxides soluble in skunk-bearing oil; substantially as described. y

In testimony whereof I have signed this specification in the presence of two witnesses.

f HERMAN FRASOH. Witnesses:

WM. A. EAs'rERnAY, O. J. HE RIPK; 

